Synthesis of Sucrose Fatty Acid Esters by Using Mixed

Home , Sucrose esters, Sucrose octaacetate

Synthesis of Sucrose Fatty Acid Esters by Using Mixed Carboxylic-fatty Anhydrides Iteb Trabelsi, Kamel Essid＊ , and Mohamed Hedi Frikha Laboratory of Organic Chemistry LR17ES08: Faculty of sciences in Sfax, Route de Soukra Km 3,5 – BP 1171-3000. Sfax. TUNISIA

Abstract: Fatty acid sugar esters are non-ionic surfactant active agents with excellent performance and many uses. This work is devoted to the synthesis of sugar esters by the esterification reaction of sugar with mixed carboxylicpalmitic anhydrides using resin Amberlyst-15 as heterogeneous acid catalyst. These anhydrides should be stable and react as acylating agents. Influence of different reaction parameters, such as the molar ratio (sucrose/anhydride), the type of solvent and the reaction time on the yield of the esterification reaction were studied. The esterification reaction of sucrose with mixed palmitic benzoic anhydride leads to a mixture of sucrose esters of palmitic acid with a good percentage of conversion. The mixed anhydride was both reactive and selective for the preparation of fatty acid ester.

Key words: fatty acid, mixed anhydride, heterogeneous acid catalyst, resin Amberlyst-15, esterification, sucrose, acylation of sucrose, sucrose fatty acid esters (SEs)

1 Introduction mixed anhydrides have been often employed in order to Sucrose fatty acid esters（SEs）, commonly called sugar obtain a high yield of ester16）. Mixed anhydrides obtained esters, are nonionic surfactants that have excellent emulsi- from two different carboxylic acids are molecules finding fying, stabilizing, detergency and other useful effect1－4）. an increasing interest in the chemical industry due to their Sugar esters are attractive because of their ready biode- high reactivity17, 18）. gradability, low toxicity and low irritation to eyes and skin5－7）. The objective in this work is to develop new techniques They have a large number of applications in industry such for the synthesis of sugar fatty acid esters by chemical as the pharmaceutical, cosmetic, detergent and food8－10）. means allowing the production of economic compounds In addition, their antimicrobial, antitumoral and insecticidal （raw materials and manufacturing processes）and environ- properties have been reported and might open new mentally friendly. markets7, 11）. The sucrose esters（SEs）are consisted from This work is devoted to the development of new reaction natural raw materials: sucrose as hydrophilic group and pathways for obtaining a sucrose fatty acid ester using fatty acids as lipophilic groups12）. Sucrose has eight hy- mixed carboxylic-fatty anhydride in the presence of ion ex- droxyl groups, which allow the formation of esters from change resins（Amberlyst-A15）as a catalyst. monoesters to octaesters with different fatty acid8, 12, 13）Su- croesters can be synthesized either by using chemical or enzymatic processes1, 2）. The chemical process is generally performed at high temperature in toxic solvents which 2 Experimental leave traces in the products, which is accompanied by low 2.1 Synthesis of sucrose octaacetate selectivity toward the various hydroxyl groups in sugars 2.1.1 Acylation reaction of sucrose solvent-free and forming coloured derivatives as side-products1－4, 11, 14, 15）. 5 g（0.014 mol）of sucrose, 100 mL（1.055 mol）of acetic Product of chemical synthesis is often an undefined and anhydride used as reactant and solvent in the reaction and complex mixture of mono-, di- and poly-esters, which is 2 g（9.4 meq/g）of resin Amberlyst A-15 as catalyst were difficult to be characterized with respect to its physical charged in a 250 ml flask. The reaction mixture was stirred properties and surfactive1, 2, 14）. Sugar esters are synthe- for 6 hours in oil bath at 50-55℃. sized by esterfication of sugars or sugar alcohols with fatty When the reaction was completed, the reaction mixture acids1）. Because the esterification is a reversible reaction, was filtered and the Amberlyst-15 washed 3 times with

＊Correspondence to: Kamel Essid, Laboratory of Organic Chemistry LR17ES08: Faculty of sciences in Sfax, Route de Soukra Km 3,5 – BP 1171-3000. Sfax. TUNISIA E-mail: [email protected] Accepted March 26, 2020 (received for review September 22, 2019) Journal of Oleo Science ISSN 1345-8957 print / ISSN 1347-3352 online http://www.jstage.jst.go.jp/browse/jos/ http://mc.manusriptcentral.com/jjocs

693 I. Trabelsi, K. Essid, and M. H. Frikha

acetic anhydride（10 mL）. The organic phase was slowly 3 Results and Discussion added to 600 mL of a mixture（water/ice）then allowed to In a previous work, we have studied the synthesis of stand for 12 hours. The syrup formed in this period was fatty esters by the esterification with mixed carboxylic pal- separated from the aqueous phase. The aqueous phase was mitic anhydrides. These anhydrides characterized by the

extracted 3 times with 30 mL of chloroform. The chloro- general formula C15H31COOCOR can be easily prepared by form extracts were combined, evaporated in vacuo and the reaction of palmitic acid with aliphatic or aromatic acid added to the syrup. The mixture obtained was then dis- chloride in the presence of triethylamine and in organic solved in 30 mL of ethanol. A small volume of water（～10 solvent19）. The esterification reaction of primary, secondary mL）was added dropwise until the solution becomes turbid. and tertiary alcohols with mixed aliphatic palmitic anhy- Crystallization of the final product was carried out at 5℃ dride and mixed aromatic palmitic anhydride was realized and white crystals were obtained. The products recrystal- in the presence of resin Amberlyst-15 as heterogeneous lized were weighed and analyzed by IR and（1H and 13C） acid catalyst. We have showed that the palmitic group of NMR spectroscopy. The yield of the acylation reaction was the mixed carboxylic palmitic anhydride was the most in- determined by calculating the ratio between the mass of volved in the esterification reaction and the leaving of the sucrose octaacetate（after recrystallization）and the theo- alkyl or aryl group of the mixed anhydride. The preferential retical mass of ester formed. esterification of alcohol was realized by the palmitic group 2.1.2 Acylation reaction of sucrose in solvent of mixed carboxylic palmitic anhydride and the obtained 5 （g 0.014 mol）of sucrose, 20 mL（0.527 mol）of acetic an- palmitic esters were produced with good yields. We have hydride and 2 （g 9.4 meq/g）of resin Amberlyst A-15 as cata- found that the mixed aliphatic palmitic anhydrides were lyst were added in a 250 mL flask. The reactants were less reactive and less selective than their mixed aromatic placed in an organic solvent such as dichloromethane, palmitic anhydrides19, 20）. Among tested mixed aromatic diethyl ether, hexane and chloroform. The mixture was palmitic anhydrides, we have chosen the mixed benzoic then stirred under refluxing of the solvent. At the end of palmitic anhydride in the esterification reaction of sucrose the reaction, the mixture reaction obtained was treated in using resin Amberlyst-15 as heterogeneous acid catalyst. the same manner as before until a dry product was obtained. The products recrystallized were weighed and ana- 3.1 Synthesis of sucrose octaacetate lyzed by IR and（1H and 13C）NMR spectroscopy. The yield We have taken first, as a simple model of anhydride: of the acylation reaction was determined by calculating the acetic anhydride in the acylation reaction of sucrose in the ratio between the mass of sucrose octaacetate（after re- presence of a catalyst. We have studied the influence of the crystallization）and the theoretical mass of ester formed. main experimental parameters such as the molar ratio （sucrose/acetic anhydride）and the type of solvent on the 2.2 Synthesis of sucroesters by mixed benzoic-palmitic yield of the acylation reaction. anhydride 3.1.1 Effect of type of solvent 3 g（8.33 10－3 mol）of crude mixed benzoic palmitic an- We have studied the effect of type of solvent on the yield hydride, 2 g, 0.5 g then 0.3 g of sucrose corresponding re- of sucroesters. The acylation reaction involves the ex-

spectively to the molar ratios（sucrose/anhydride）（ 1:1.5）, change of the（OH）group of the sucrose by the（OCOCH3）（1:6）and（1:10）and 2 g（9.4 meq/g）of Amberlyst-15 are group of the acetic anhydride in the presence of an ion ex- were stirred under reflux of organic solvent such as hexane change resin Amberlyst-15 as heterogeneous catalyst. The and cyclohexane. After completion of the reaction, the re- reaction mixture was stirred for 6 hours at a temperature action mixture was filtered and the Amberlyst-15 resin was of 50-55℃（ without solvent）or under reflux of solvent as washed with the organic solvent（20 mL）. The solvent was indicated in Scheme 1. then evaporated to dryness and the crude product was The acylation reaction was carried out with a large weighed and analyzed by IR, 1H NMR and 13C NMR. excess of acetic anhydride used as reactant and solvent. Then, we introduced an organic solvent in the reaction 2.3 Spectroscopic analysis medium to facilitate the contact between the reactants and The FT-IR spectra of the crude products were recorded to ensure the better reactivity. Solvents of different polari- on a spectrometer type Perkin Elmer Spectrum version 10. ties were used while keeping the same procedure. The The NMR spectra of the crude products were recorded yields of recrystallized products were resumed in the Table

in solution in CDCl3 on a spectrometer type Bruker Avance 1 and the structure of these products was confirmed by IR III HD（1H at 400 MHz and 13C at 100 MHz）. and（1H and 13C）NMR analysis. The IR spectra of recrystallized products show the disappearance of the C＝O absorption bands characteristic of the acetic anhydride and also the disappearance of the OH absorption band of the sucrose at 3400 cm－1. These

694 J. Oleo Sci. 69, (7) 693-701 (2020) New Reaction for Obtaining a Sucrose Fatty Acid Ester Using Mixed Carboxylic-fatty Anhydride

Scheme 1 The acylation reaction of sucrose with acetic anhydride.

Table1 Yields of sucrose octaacetate realized without or with solvent. Volume of solvent Volume of acetic Entry Acylation Solvent Yield% (mL) anhydride (mL) 1 Without solvent Anhydride acetic － 100 37 2 Chloroform 20 20 38 3 Dichloromethane 20 20 25 With solvent 4 Diethyl ether 20 20 22 5 Hexane 20 20 43

Table 2 Yields of sucrose octaacetate realized in the mixture solvent（chloroform/hexane）. Mixture of solvent Entry Yield% Chloroform (mL) Hexane (mL) 1 0 20 43 2 5 15 21 3 10 10 27 4 15 5 22 5 20 0 38 spectra show the appearance of new C＝O absorption band entry 2: 43％ and entry 5: 38％）. A low yields is obtained corresponding to sugar ester at 1756 cm－1. The 13C NMR in the case of where the reaction is carried out in dichloro- spectrum is in agreement with the structure of the desired methane and diethyl ether（Table 1, entry 3: 25％ and compound. The 8 peaks corresponding to 8 carbonyls（C＝ entry 4: 22％）. O）are observed between 165 and 167 ppm which proves However, it is pertinent to note that the acylation in that all the OH groups of sucrose are acylated. The analysis hexane results in a significant yield than when performed by 1H NMR confirmed also that the recrystallized product in chloroform. Chloroforem and hexane are solvents of dif- is sucrose octaacetate. The 1H NMR spectrum shows the ferent polarities. This led us to keep the same experimental signals between 4 and 5.7 ppm corresponding to 14 protons protocol, and try to improve the ester yield, by acting on of the sucrose molecule and a multiplet at 2.1 ppm corre- the polarity of the reaction medium. We carried out a series sponding to 24 protons relative to 8 CH3 groups. of acylation reactions in a 20 mL mixture of the solvent The yield of the recrystallized product obtained by the （hexane/chloroform）by varying the volume ratio（chloro- acylation of sucrose with acetic anhydride without solvent form/hexane）as shown in Table 2. is 37％（ Table 1, entry 1）. Solvents of different polarities It is found that the variation in the volume ratio of the were introduced into the reaction mixture to facilitate the solvent mixture（chloroform/hexane）in the acylation reac- contact between the reactants. From the results given in tion did not impovre the yield of sucrose octaacetate（Table the Table 1, the yield obtained in the case of acylation with 2, entry 2: 21％, entry 3: 27％ and entry 4: 22％）. The best acetic anhydride, catalyzed by the Amberlyst-15 resin, yield of sucoester is obtained in the case where the reac- does not exceed 43％ after treatment and the purification tion is carried out in 20 mL of hexane（Table 2, entry 1: of the crude product. The best yield of sucrose octaacetate 43％）. is obtained in the case where the reaction is carried out in 3.1.2 Effect of the molar ratio（sucrose/anhydride） hexane followed by the reaction in chloroform（Table 1, We have studied the effect of the molar ratio（sucrose/

695 J. Oleo Sci. 69, (7) 693-701 (2020) I. Trabelsi, K. Essid, and M. H. Frikha

Table 3 Effect of molar ratio（sucrose/anhydride）on the yield of acylation. Volume of acetic Molar ratio Entry Solvent Yields (%) anhydride (mL) (sucrose/anhydride) 1 10 1 : 19 － 2 Chloroform 20 1 : 38 38 3 30 1 : 57 32 4 10 1 : 19 － 5 Hexane 20 1 : 38 43 6 30 1 : 57 34

anhydride）on the yield of sucroesters. We have varied the （sucrose/anhydride）have been varied to find the best con- molar ratio（sucrose/anhydride）fixing the other experimen- ditions which favor the progress of this reaction. tal conditions such as the volume solvent at 20 mL, time Sucrose contains three primary and five secondary hy- réaction and temperature to improve the yield of sucrose droxyl groups. We have assumed that the esterification of octaacetate. Spectroscopic analysis IR and（1H and 13C） the OH groups of sucrose by the palmitic group. The pal- NMR show that que the recrystallized products are sucrose mitic group of the mixed carboxylic palmitic anhydride was octaacetate. The yields of sucrose octaacetate were the most involved in the esterification reaction of primary resumed in the Table 3. and secondary alcohols of and the leaving of the aryl group The best yield of sucoester is obtained in the case where of the mixed benzoic palmitic anhydride. In addition, the the reaction is carried out in hexane with a molar ratio formation rate of benzoic ester was much slower than that （sucrose/anhydride）that equal to 1:38（Table 3, entry 5: of aliphatic acid ester when we used the mixed anhydrides 43％）. Less important yield is obtained in the case where as reagents of esterification19, 20）. the reaction is carried out in choloroform（Table 3, entry 2: 3.2.1 Effect of molar ratio（sucrose/anhydride）and reaction 38％）. When the molar ratio（sucrose/anhydride）is in- time in hexane creased to（1:59）, the yield of sucrose octaacetate decreas- The action of mixed benzoic-palmitic anhydride on es in the case where the reaction is carried out in hexane sucrose with the molar ratios（sucrose:anhydride）（ 1:1.5） and chloroform（Table 3, entry 3: 32％ and entry 6: 34％）. and（1:6）in the presence of resin Amberlyst-15 was stirred The variation in molar ratio（sucrose/anhydride）in the under reflux hexane for 16 hours. During this period, sucrose acylation reaction did not improve the yield of su- Samples are taken at different times（6 h, 8 h, 10 h, 12 h croesters. and 16 h）for both reactions. Each sample is analyzed by Acylation of sucrose with acetic anhydride in the pres- IR. The IR spectra show no difference for each sample at（6 ence of an ion exchange resin Amberlyst-15 as heteroge- h, 8 h, 10 h, 12 h and 16 h）for both reactions（Fig. 1 and neous catalyst leads to a sucrose octaacetate with a yield Fig. 2）. of 43％. The reaction is carried out in 20 mL of hexane and The IR spectra（Fig. 1 and Fig. 2）show the disappear- with molar ratio（sucrose/anhydride）（ 1:38）. ance of the C＝O absorption bands of the mixed benzoic It is found that the best acylation yield exceeds slightly palmitic anhydride at 1725 and 1795 cm－1 and the disap- 40％（ entry: 1）after treatment and purification of the crude pearance of the OH absorption band at 3400 cm－1 of reaction. This is probably due to side reactions that can sucrose. These spectra also show the appearance of two occur in parallel with acylation as hydrolysis and sucrose news C＝O absorption bands at 1744 cm－1 of sugar ester of polymerization. Although we worked in an anhydrous the palmitic acid and at 1685 cm－1 of palmitic acid and medium with well-dried reagents and distilled solvents（to benzoic acid. It has a OH broad band absorption between remove all traces of water）, the risk of these reactions is 2550 and 2670 cm－1 of acid and a C-O absorption band always maintained. between 1150 and 1300 cm－1 of the sucroester. These spectra show, in fact, just traces of palmitic acid 3.2 Synthesis of sugar esters by mixed benzoic-palmitic sugar ester. It is found that increasing the ratio（sucrose/ anhydride anhydride）from（1:1.5）to（1:6）causes a slight increase in In the second part, the esterification reaction is carried the C＝O absorption band characteristic of the sugar ester out by the action of the benzoic palmitic anhydride already of the palmitic acid. prepared as indicated in the article19, 20）on sucrose in the 3.2.2 Effect of molar ratio（sucrose/anhydride）in cyclohex- presence of an ion exchange resin A-15 as a catalyst in an ane organic solvent. The main experimental parameters such To improve the yield of the sucrose ester, the hexane as the type of solvent, the reaction time and the molar ratio organic solvent was changed by cyclohexane. The esterifi-

696 J. Oleo Sci. 69, (7) 693-701 (2020) New Reaction for Obtaining a Sucrose Fatty Acid Ester Using Mixed Carboxylic-fatty Anhydride

Fig. 1 IR spectrum of the crude product obtained with a molar ratio（sucrose/anhydride）（ 1:1.5）in hexane.

Fig. 2 IR spectrum of the crude product obtained with a molar ratio（sucrose/anhydride）（ 1:6）in hexane.

cation reaction of sugar is carried out with a molar ratio 2670 cm－1 of acid and a C-O absorption band located （sucrose/anhydride）（ 1:6）then（1:10）for 6 h. The products between 1150 and 1300 cm－1 of sucroester. obtained at the end of the reactions are analyzed by IR as The IR spectra（Fig. 3 and Fig. 4）of the crude products shown in Fig. 3 and Fig. 4. obtained at the end of the reaction, when the molar ratio The IR spectra（Fig. 3 and Fig. 4）show the absence of （sucrose/anhydride）of（1:6）to（1:10）is increased, show an the C＝O absorption bands of the mixed benzoic palmitic increase in the C＝O absorption band at 1744 cm－1 of the anhydride at 1725 and 1795 cm－1 and the absence of the sugar ester of palmitic acid. OH absorption band at 3400 cm－1 of sucrose. These The crude product obtained with a molar ratio（sucrose/ spectra also show the appearance of two news C＝O ab- anhydride）（ 1:10）in cyclohexane is then purified by column sorption bands at 1744 cm－1 of sugar ester of palmitic acid chromatography to obtain the sugar ester of palmitic acid. and at 1685 cm－1 of palmitic acid and benzoic acid. They The crude product dissolved in the minimum of the dichlo- present a OH broad band absorption beteween 2550 and romethane solvent is deposited at the top of the column.

697 J. Oleo Sci. 69, (7) 693-701 (2020) I. Trabelsi, K. Essid, and M. H. Frikha

Fig. 3 IR spectrum of the crude product obtained with a molar ratio（sucrose/anhydride）（ 1:6）in cyclohexane.

Fig. 4 IR spectrum of the crude product obtained with a molar ratio（sucrose/anhydride）（ 1:10）in cyclohexane.

The column is washed with a solvent mixture（dichloro- arising from the palmitic acid chain. methane/ethanol）（ 90/10, v/v）. The palmitic acid sugar The 13C NMR spectrum of the palmitic acid sucrose ester ester obtained is a white solid and then analyzed by IR, 1H （Fig. 6）shows, in particular, peaks between 14 and 35 ppm 13 and C NMR as shown in Fig. 5, Fig. 6 and Fig. 7. which correspond to the carbons of CH3 and CH2 groups of The IR spectrum of the sugar ester of palmitic acid（Fig. the palmitic acid, peaks between 55 and 110 ppm which 5）shows the disappearance of the C＝O absorption band at correspond to the carbons of sucrose, peaks between 125 1685 cm－1 of benzoic acid and palmitic acid and the and 135 ppm which correspond to the carbons of benzoic absence of the OH absorption band at 3400 cm－1 of acid（-C＝, -CH＝）and 8 peaks corresponding to C＝O sucrose. It also shows the appearance of the C＝O absorp- groups between 170 and 175 ppm. It appears that in our tion band at 1742 cm－1, the C-O absorption band at 1162 operating conditions all OH groups available in the mole- cm－1 relating to the function of the sugar ester of palmitic cule of sucrose have been esterified. acid and the C-H absorption band between（2850-2950 cm－1） The 1H NMR spectrum of sucrose ester of palmitic acid

698 J. Oleo Sci. 69, (7) 693-701 (2020) New Reaction for Obtaining a Sucrose Fatty Acid Ester Using Mixed Carboxylic-fatty Anhydride

Fig. 5 IR spectrum of the sugar ester of palmitic acid.

13 Fig. 6 C NMR spectrum of the sugar ester of palmitic acid.

（Fig. 7）shows the protons of sucrose coming of the esteri- 4 Conclusion fication of mixed benzoic palmitic anhydride. This spec- This paper describes the new techniques for the synthe- trum shows that the purified product is a mixture of pal- sis of sugar fatty acid esters by chemical means. We have mitic acid sucroesters. It shows the presence of three studied the synthesis of sucrose esters by esterification of doublets of a single proton of hydrogen atom（1H）of sucrose sucrose using two types of anhydride: symmetrical anhy- skeleton at 5.9, 6.4 and 6.6 ppm. The polyfunctionality of dride（acetic anhydride）and mixed anhydride（mixed pal- sucrose plays a very important role in the reaction com- mitic benzoic anhydride）in the presence of an ion ex- plexity. The physicochemical properties of sucrose are change resin Amberlyst-15 as a heterogeneous catalyst. We complex. The multifunctional structure posed difficulties have improved the yield of the sugar ester by varying in the experimental study. several experimental parameters such as solvent type, reaction time and molar ratio（sucrose/anhydride）. IR and（1H and 13C）NMR spectroscopic analysis show that the esterification reaction of sucrose with acetic anhydride leads to a

699 J. Oleo Sci. 69, (7) 693-701 (2020) I. Trabelsi, K. Essid, and M. H. Frikha

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